A. Chaturvedi

SYNTHESES AND SPECTROSCOPIC STUDIES OF 2-ALKYLENE DITHIOPHOSPHATO-1,3,2- DIOXARSOLANES AND -ARSENANES

Abstract Compounds of the type [where G = [sbnd]CMe2CMe2[sbnd],[sbnd]CH2CMe2CH2, G = [sbnd]CMe2CMe2[sbnd]CH2CMe2,CH2 [sbnd],[sbnd]CH2CH2CHMe[sbnd], and [sbnd]CMe2CH2,CHMe[sbnd]] have been synthesized by the reactions of ammonium salts of alkylene dithiophosphates with 2-chloro-1,3,2-dioxarsolanes and -arsenanes. The new derivatives are yellow crystalline solids, soluble in common organic solvents, monomeric in nature, and are characterized by elemental analyses, molecular weight measurements, IR and multinuclear NMR (1H, 13C, and 31 P) spectroscopic data.

Cleavage Reactions of Triphenylantimony with Dialkyl (or Alkylenyl) Dithiophosphoric Acids a

Abstract Triphenylantimony reacts with dialkyl (or alkylenyl) dithiophosphoric acids in 1:1 and 1:2 molar ratio to form complexes of the types Ph3-h Sb(S2P(OR)2]n and Ph3-n sb[S2 ]n (R = Pr-n, Pr-i, Bu-i; G = -CMe2CMe2, -CH2CMe2CH2-, - CMe2CH2CHMe-, n = 1,2) by the cleavage of antimony-carbon bonds. The complexes are colourless powdery solids, soluble in common organic solvents, monomeric in nature and have been characterized by various physico-chemical and spectroscopic [IR, NMR (1H, 13C, 31P)] techniques. a This article is dedicated to the late Prof. G. Srivastava, Department of Chemistry, University of Rajasthan, Jaipur, India.

SYNTHESES AND PROPERTIES OF MIXED LIGAND COMPLEXES OF DIORGANOTIN(IV): PART I. β-DIKETONATO DIORGANOTIN DIALKYL (OR ARYL) DITHIOPHOSPHATES AND 1-β-DIKETONATO-3-DIALKYL DITHIOPHOSPHATO TETRABUTYL DISTANNOXANES

Abstract The mixed ligand complexes of the type R2′Sn[R″COCHCOR″] [S2P(OR‴)2] and [(R‴O)2S2P] R2′SnOSn R2′ [R″COCHCOR″] have been prepared by the reaction of diorganotin oxide (R′ = Bu, Ph) or chloride (R′ = Me) with β-diketones and dialkyl (or aryl) dithiophosphoric acids in 1:1:1 and 2:1:1 molar ratios is refluxing benzene. The products formed are monomeric, non volatile, yellow colored viscous liquids or sticky solids, soluble is common organic solvents and exhibit high sensitivity towards atmospheric moisture. These complexes have been characterized by elemental analyses, molecular weight measurements, IR and NMR (1H, 31p and 119Sn) spectral data. On the basis of 119Sn NMR studies, it was postulated that there might be disproportionation which led to the formation of mixture with fast exchange between Sn—S and Sn—O linkages.

SYNTHESES AND SPECTROSCOPIC STUDIES OF DIORGANOTIN BIS-O-ALKYL PHOSPHONATES

Abstract Diorganotin bis-O-alkyl phosphonates, R2Sn[O2P(H)OR′]2 (R = Me, Et; R′ = Me, Et, Bu, Ph) have been obtained in quantitative yield by reacting sodium salts of O-alkyl phosphonate with diorganotin dichloride. The derivatives are white colored, hydrolytically stable powdery solids, soluble in methanol (when freshly prepared) and are characterized by various physico-chemical as well as spectroscopic IR, NMR (1H, 31P and 119Sn) studies which are consistent with 6-coordinated tin atom.

TETRAPHENYL PHOSPHONIUM AND ARSONIUM SALTS OF ALKYLENE DITHIOPHOSPHATO MOIETIES

Abstract Complexes of the type [Ph4M]+[S2POGO]− (M[dbnd]Por As; G= -CMe2CH2CHMe-, CH2CMe2CH2− , -CH2CEt2CH2− , -CMe2CMe2− and -CH2CH2CHMe-) have been synthesized by the reactions of tetraphenyl phosphonium and arsonium chloride with ammonium alkylene dithiophosphates. The derivatives have been chracterized by elemental analyses, molar conductance spectroscopic (IR, 1H and 31P NMR) studies.

Synthesis and Properties of Mixed Ligand Complexes of Diorganotin (IV): Part (V): Synthesis and Characterisation of Antifungal Acetylacetonato Diorganotin (IV)- O -Alkyl Trithiophosphates

Some antifungal mixed ligand complexes of the type R 2 Sn[SSH(S)POR′] [MeCOCHCOMe] have been synthesised by the reactions of diorganotin dichloride, R 2 SnCl 2 (R = Me, Bu, Ph) with acetyl acetone and O-alkyl trithiophosphates, R′OPS 3 K 2 (R′ = Me, Et, Pr i , Bu i , Ph) in 1:1:1 molar ratio in refluxing benzene. The products formed are monomeric, light yellow colored crystalline solids, soluble in common organic solvents and exhibit high sensitivity towards atmospheric moisture. The complexes have been characterised by elemental analysis (S,Sn), molecular weight measurements, IR and NMR ( I H, 31 P, 119 Sn) spectral studies. On the basis of spectral studies, it is postulated that acetyl acetonate and O-alkyl trithiophosphate moieties are bidentate and tin is hexacoordinated in nature. On the basis of 119 Sn NMR spectral studies, it is postulated that an equilibrium, with the results of disproportion is established. It is observed that when these compounds are applied in the form of dilute solution to various concentrations, they show their effectiveness against powdery mildew disease at a fixed interval of days.

O,O′-dialkyl and alkylene dithiophosphate derivatives of silver(I). X-ray crystal structure of [Ag{S2POCH2CMe2CH2O} PPh3]2 · 2H2O

Silver(I) dialkyl/alkylene dithiophosphates of the types [Ag{S2P(OR)2}] and [Ag{S2P(OGO)}] (where R = –Prn; G = –CMe2CH2CHMe–, –CH2CMe2CH2–, –CMe2CMe2– or –CH2CH2CHMe–) have been prepared by treating an aqueous solution of AgNO3 with ammonia salts of the respective dithiophosphoric acid. The derivatives form 1:1 adducts readily with 2,2′-bipyridine or Ph3P in CH2Cl2 solution. These novel complexes have been characterized by elemental analyses, molecular weight measurements and spectral (i.r., 1H- and 31P-n.m.r.) studies. The crystal structure of [Ag{S2POCH2CMe2CH2O · PPh3]2 · 2H2O exhibits an unsymmetrical attachment of the silver(I) to the ligand moiety.

Boron Spirochelates Derived from 24Sopropoxy-4H-1,3,2-Benzodioxaborin

Abstract 2-(β-diketonato -4H- 1,3,2b enzodioxaborin, , (R = R′ Me, Ph), 2-(N-alkyIsalicylaldimino)-4H-1,3,2,-benzodioxaborin, , (R = Me, Et, n-Pr, n-Bu, Ph) and 2-(4-alkylamino-3-pentene-2-on)-4H-1,3,2,-benzodioxaborin, (R = Me, Et, CH2Ph, Ph) obtained by the reactions of 2-isopropoxy-4H-1,3,2-benzodioxaborin with B-diketonates, N-alkylsalicylaldimines and 4-alkyiamino-3-pentene-2-ones, respectively, are white or yellow colored monomeric solids. These compounds have been characterized by elemental analyses, molecular weight measurements, IR and NMR (1H and 11B) data. On the basis of the above studies the tetra-coordinated nature of boron has been established in these compounds.

Syntheses and spectroscopic studies of diphenylphosphinato derivatives of boron

Summary2-Diphenylphosphinato-1,3,2-dioxaborolanes and -borinanes of the type (whereG = -CH2CHMe-, -CH2CH2CH2-, -CH2CH2CHMe-,-CMe2CMe2-, -CMe2CH2CHMe-,-CH2CMe2CH2-, -CH2CEt2CH2-, and -C6H4-) are obtained by the reaction of diphenylphosphinic acid with the corresponding 2,2′-oxo-bis-1,3,2-dioxaborolanes and-borinanes. The products are white crystalline solids, which have sharp melting points and are hydrolytically stable. They have been characterized by elemental analysis, IR and multinuclear NMR (11B,31P, and119Sn) studies. The data suggest structures with monodentate phosphinato moieties and 3-coordinated boron atoms.Zusammenfassung2-Diphenylphosphinato-1,3,2-dioxaborolane und -borinane des Typs (mitG = -CH2CHMe-, -CH2CH2CH2-,-CH2CH2CHMe-, -CMe2CMe2-,-CMe2CH2CHMe-, -CH2CMe2CH2-, -CH2CEt2CH2- und C6H4) erhält man durch Reaktion von Diphenylphosphinsäure mit den entsprechenden 2,2′-Oxo-bis-1,3,2-dioxaborolanen und -borinanen. Die Produkte sind weiße, kristalline, hydrolyseunempfindliche Festkörper. Sie wurden mittels Elementaranalyse, IR-Spektroskopie und multinuklearer NMR-Spektroskopie (11B,31P und119Sn) charakterisiert. Die Resultate legen Strukturen mit monodentaten Phosphinatoeinheiten und dreifach koordinierten Boratomen nahe.

O-Alkyl trithiophosphate derivatives of triorganotin(IV) and S-alkyl trithiophosphate derivatives of diorganotin(IV) chloride

Reactions of triorganotin chlorides with potassium salt of O-alkyl trithiophosphate [ROP(S)(SK)2; R = Me, Pri, Ph] in 2:1 molar ratio in anhydrous benzene yield triorganotin O-alkyl trithiophosphate of the type ROP(S) [SSnR′3]2 R = Me, Pri; Ph, R′ = Prn, Bun, Ph] which are found to be monomeric in nature. These complexes are soluble in common organic solvents. Similar reactions of diorganotin chloride with dipotassium salt of S-alkyl trithiophosphate yield diorganotin-S-alkyl trithiophosphate of the type [(RS)P(O)S2]2SnR′2; R = Me, Pri; R′ = Me, Et, Ph, which also are found to be monomeric in nature and are soluble in common organic solvents. The newly synthesized derivatives have been characterized by physicochemical and spectroscopic techniques, IR, NMR (1H, 31P, and 119Sn).